Comprehensive two-dimensional gas chromatography (GC×GC) measurements of volatile organic compounds in the atmosphere

During the MINOS campaign in August 2001 comprehensive two-dimensional gas chromatography (GC×GC) was applied to the in situ measurements of atmospheric volatile organic compounds (VOCs) at the Finokalia ground station, Crete. The measurement system employs a thermal desorption unit for on-line sampling and injection, and a GC×GC separation system equipped with a flame ionization detector (FID) for detection. The system was optimized to resolve C7 − C14 organic components. Two-dimensional chromatograms from measurements of Finokalia air samples show several hundred wellseparated peaks. To facilitate peak identification, cartridge samples collected at Finokalia were analyzed using the same GC×GC system coupled with a time-of-flight mass spectrometer (TOF-MS). The resulting mass spectra were deconvoluted and compared to spectra from a database for tentative peak identification. About 650 peaks have been identified in the two-dimensional plane, with significant signal/noise ratios (>100) and high spectra similarities (>800). By comparing observed retention indices with those found in the literature, 235 of the identifications have been confirmed. 150 of the confirmed compounds show up in the C7 − C14 range of the chromatogram from the in situ measurement. However, at least as many peaks remain unidentified. For quantification of the GC×GC measurements, peak volumes of measured compounds have been integrated and externally calibrated using a standard gas mixture.